Method for eliminating mercaptan from crude gas

ABSTRACT

This invention relates to a process for cleaning gas, in particular hydrocarbonaceous gas such as e.g. natural gas, which is contaminated with sulfur in the form of H 2 S and mercaptans as well as CO 2 .  
     To remove the undesired sulfur-containing substances in the form of H 2 S and mercaptan from crude gas, it is proposed in accordance with the invention that the crude gas is introduced into an absorption and regeneration column and washed therein, three gas streams being withdrawn from this absorption and regeneration column, a first exhaust gas stream being introduced into a Claus plant, a second sour gas stream with a low H 2 S concentration being introduced into another absorption plant, and a third gas stream, the valuable gas with the mercaptans, being cooled and supplied to an adsorption plant, that from this adsorption plant a cleaned valuable gas is withdrawn, and a mercaptan-containing gas stream is subjected to washing, that this concentrated mercaptan-containing gas is supplied to the Claus plant.

This invention relates to a process of cleaning gas, in particular hydrocarbonaceous gas such as e.g. natural gas, which is contaminated with sulfur in the form of H₂S and mercaptan as well as CO₂.

The document WO 97/26069 describes a process of cleaning carbon dioxide and sulfur-containing gases, in which there are sulfur-contaminated impurities in the form of mercaptans and H₂S. In a first absorption, the sulfur-contaminated impurities are removed from the gas, in order to produce a clean gas stream and a sour gas stream, the sour gas being hydrogenated in order to convert a major amount of mercaptans to H₂S. The hydrogenated sour gas is introduced into a second absorption/regeneration plant, in which the sour gas is separated into a first gas stream rich in H₂S, which is introduced into a Claus plant, and a second gas stream containing little H₂S, which is supplied to the postcombustion. The Claus plant is followed by a tail gas aftertreatment, in wich the H₂S is reduced further and a gas rich in H₂S is withdrawn.

What is disadvantageous in this process is the too small amount of sulfur and mercaptans which can be removed from the gas. In accordance with the prior art, it is only possible with a large effort to remove the sulfur from the crude gas for more than 95 wt-%.

It is the object underlying the invention to create an improved process for cleaning hydrocarbonaceous gas, in which the undesired sulfur-containing substances in the form of H₂S and mercaptan are removed.

In accordance with the invention, this object is solved in that crude gas is introduced into an absorption and regeneration column and washed therein, three gas streams being withdrawn from this absorption and regeneration column, a first exhaust gas stream being introduced into a Claus plant, a second sour gas stream with a low H₂S concentration of 10-30 vol-% being introduced into another absorption plant, and a third gas stream, the valuable gas with the mercaptans, being cooled and supplied to an adsorption plant, that from this adsorption plant a sweet gas is withdrawn and a gas stream containing mercaptan is subjected to washing. As washing stage, there is preferably used a physical washing stage, e.g. a Purisol plant, with which a small amount of gas with a high concentration of mercaptan is introduced into the Claus plant and part of the coadsorbed valuable gas from the regeneration of the adsorption plant is recovered as fuel gas. In the Claus plant, the mercaptan gas is burnt completely.

Due to the fact that before being introduced into the Claus plant, the second sour gas stream is first fortified in an absorption and the solution is regenerated in a fortification washing stage, the Claus plant can be designed smaller, as the sour gas stream has a higher concentration of H₂S. The processing of concentrated H₂S-containing gas and the mercaptan stream in the Claus plant as well as the processing of the gas stream from the first absorption and of the Claus exhaust gas in a tail gas washing stage increases the degree of sulfur recovery of the entire plant.

To achieve that the absorption plant for the sour gas to be fortified consumes less lye and only one regeneration column is required, the H₂S-containing solution is withdrawn from the absorption plant, which is disposed behind the hydrogenation of the residual Claus gas, and introduced into the absorption plant for fortifying the sour gas.

The degree of sulfur recovery is increased in that the gas from the absorption of the fortification is introduced into the hydrogenation, in order to convert sulfur components into H₂S, and subsequently into the absorption of the tail gas aftertreatment.

Embodiments of the process will be explained by way of example with reference to the drawing.

Through line (1), crude gas is introduced into a first washing stage comprising an absorption and regeneration column (2) and washed therein. A first exhaust gas stream (5) from the regeneration is directly introduced into a Claus plant (14). This exhaust gas stream (5) chiefly consists of up to 80 vol-% hydrocarbon and up to 20 vol-% CO₂ with small amounts of mercaptans (up to 0.3 vol-%) and H₂S (up to 5 vol-%).

A second sour gas stream (4) with a low H₂S concentration of up to 30 vol-% H₂S is introduced into another absorption plant (15) and fortified there with a non-loaded solvent from lines (26) and (27). From the absorption plant (15), the solvent (16) loaded with H₂S is introduced into a regeneration plant (17). The gas (up to 97 vol-% CO₂ and 0.2 vol-% mercaptan) from the absorption plant (15) is supplied to a hydrogenation (22) via line (18).

From the regeneration (17), sour gas with a high H₂S concentration of up to 60 vol-% H₂S is introduced into the Claus plant (14) via line (19).

From the absorption and regeneration column (2) a third gas stream (3), the valuable gas with the largest content of mercaptans, is withdrawn, cooled (6) and supplied to an adsorption (8) via line (7). From this adsorption (8), the valuable gas is supplied to further processes, e.g. a liquefaction, via line (9). The mercaptan-containing gas stream (10) is subjected to a physical washing stage, from which the coadsorbed valuable gas is recovered as fuel gas via line (12), and the highly concentrated mercaptan gas is supplied to the Claus plant (14) via line (13). The mercaptan stream is recovered in the regeneration of the Purisol solvent. The amount is small, but with a very high mercaptan concentration of 10 vol-% to 60 vol-%. As an alternative to the Purisol plant (11), another physical or physical-chemical washing stage is possible. However, the same have the disadvantage that too much CH₄ is absorbed. In the Claus plant (14), the mercaptan is burnt completely. The SO₂ obtained therefrom is reacted with the H₂S from the sour gas of line (19) to form sulfur. The liquid sulfur obtained is withdrawn via line (21) and supplied to a further use. Thus, a high degree of sulfur recovery is achieved. The Claus plant (14) is a plant known per se, which consists of a combustion furnace as well as a plurality of catalytic reactors for performing the reaction. In the Claus plant (14), there is always obtained a so-called residual Claus gas, which apart from non-condensed elementary sulfur contains unreacted sulfur dioxide and H₂S. This residual gas is withdrawn via line (20) and subjected to an aftertreatment, in order to increase the degree of sulfur recovery. Via line (20), the residual Claus gas is supplied to a hydrogenation plant (22), which is also supplied with the gas from the absorption plant (15) via line (18). In the hydrogenation, SO₂ is converted to H₂S and supplied to an absorption plant (24) via line (23). From the absorption plant (24), a solution is introduced into the fortification absorption (15) via line (26) for the further absorption of H₂S. The remaining H₂S-containing gas is withdrawn from the absorption plant (24) via line (25) and supplied to a combustion.

EXAMPLE

The following Table shows an analysis of the gas streams in the individual lines. The liquid process streams in lines (16), (26), (27) and (28) are not shown. Line No.: 1 3 4 5 7 Process First Exhaust Cooled stream Crude Gas Valuable Gas Sour gas Gas Stream Valuable Gas Components Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% CO₂ 21680 2.59 41 0.005 21542.7 75.90 97.13 13.10 41 0.005 N₂ 29102 3.48 29092 3.59 9.88 1.33 29092 3.59 CH₄ 705460 84.26 704924 86.97 38.41 81.43 498.24 67.22 704924 87.06 C₂H₆ 45661 5.45 45610 5.63 5.49 5.27 45.08 6.08 45610 5.63 C₃H₈ 18593 2.22 18573 2.29 2.74 2.15 17.35 2.34 18573 2.29 i-C₄ 2981 0.36 2979 0.37 2.70 0.36 2979 0.37 n-C₄ 4333 0.52 4329 0.53 3.91 0.53 4329 0.53 i-C₅ 1203 0.14 1202 0.15 1.11 0.15 1202 0.15 n-C₅ 1040 0.12 1039 0.13 0.96 0.13 1039 0.13 C₆ cut 751 0.09 750 0.09 0.71 0.10 750 0.09 C₇ cut 379 0.05 379 0.05 0.28 0.04 379 0.05 C₈ 140 0.02 140 0.02 0.14 0.02 140 0.02 C₉ 93 0.01 93 0.01 0.07 0.01 93 0.01 H₂S 5851 0.699 2 0 5816.5 20.49 31.74 4.28 2 0 COS 2.5 0.000 0.8 0 1.7 0.006 0.01 0.002 0.8 0 CH₃SH 21.8 0.003 17.0 0.002 4.5 0.016 0.21 0.028 17.0 0.002 C₂H₅SH 117.2 0.014 93.0 0.011 23.1 0.081 1.12 0.151 93.0 0.011 C₃H₇SH 47.7 0.006 45.0 0.006 2.3 0.008 0.41 0.055 45.0 0.006 C₄H₉SH 5.0 0.001 4.7 0.001 0.3 0.001 0.04 0.006 4.7 0.001 CS₂ SO₂ SX CO H₂ O₂ H₂O 1182 0.15 946 3.33 30.16 4.07 383 0.05 Line No.: 9 10 12 13 18 Mercaptan- Enriched Residual Process Containing Mercaptan Absorption Stream Sweet Gas Gas Stream Fuel Gas Gas Gas Components Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% CO₂ 41 0.005 16588 96.11 N₂ 29077 3.60 7814.5 29.35 7812.2 29.65 2.3 0.82 CH₄ 704571 87.12 18552.5 69.68 18446.7 70.01 105.8 37.00 38 0.22 C₂H₆ 45587 5.64 22.8 0.09 22.3 0.08 0.5 0.17 5 0.03 C₃H₈ 18559 2.29 13.9 0.05 11.9 0.05 2.0 0.70 3 0.02 i-C₄ 2977 0.37 1.5 0.01 1.0 0 0.4 0.16 n-C₄ 4327 0.53 2.2 0.01 1.8 0.01 0.4 0.13 i-C₅ 1201 0.15 0.6 0 0.3 0 0.3 0.12 n-C₅ 1038 0.13 0.5 0 0.2 0 0.3 0.11 C₆ cut 749 0.09 1.3 0 1.3 0.45 C₇ cut 377 0.05 2.1 0.01 2.1 0.73 C₈ 138 0.02 1.7 0.01 1.7 0.61 C₉ 89 0.01 4.3 0.02 4.3 1.51 H₂S 2.4 0.000 8.6 0.05 COS 0.8 0.000 1.5 0.009 CH₃SH 0.2 0.000 16.8 0.063 0.2 0.001 16.6 5.80 4.1 0.024 C₂H₅SH 1.4 0.000 91.6 0.344 0.3 0.001 91.3 31.95 20.7 0.120 C₃H₇SH 0.7 0.000 44.3 0.167 0.9 0.003 43.4 15.20 2.1 0.012 C₄H₉SH 0.1 0.000 4.6 0.017 0.7 0.003 4.0 1.39 0.2 0.001 CS₂ 10.0 0.03 SO₂ 74.0 0.20 SX 15.0 0.04 CO 852.0 2.30 H₂ 501.0 1.35 O₂ H₂O 0.8 0.000 51 0.19 51 0.19 9 3.16 588 3.41 Line No.: 19 20 23 25 21 Concentrated H₂S- Residual Hydrogenated Process containing Claus Residual Liquid stream Gas Gas Claus Gas Exhaust Gas Sulfur Components Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% Nm³/h Vol-% CO₂ 7550.4 53.02 7909 21.36 25955.6 42.66 23360 47.71 N₂ 17518 47.31 21717.3 35.69 21717 44.36 CH₄ 41.3 0.07 41 0.08 C₂H₆ 20.4 0.03 20 0.04 C₃H₈ 4.3 0.01 4 0.01 i-C₄ n-C₄ i-C₅ n-C₅ C₆ cut C₇ cut C₈ C₉ H₂S 6238.5 43.80 148 0.40 455.2 0.75 24.48 0.05 0.09 0.00 COS 0.2 0.001 65 0.18 4.6 0.01 4.56 0.01 CH₃SH 0.5 0.003 0.97 0.00 0.97 0.00 C₂H₅SH 2.3 0.016 5.78 0.01 5.78 0.01 C₃H₇SH 0.2 0.002 0.49 0.00 0.49 0.00 C₄H₉SH 0.0 0.000 CS₂ 10 0.03 SO₂ 74 0.20 SX 15 0.04 8579.2 100.00 CO 852 2.30 149.73 0.25 149.73 0.31 H₂ 501 1.35 1380.53 2.27 1380.53 2.82 O₂ H₂O 450 3.16 9936 26.83 11103.9 18.25 2251 4.60

Corresponding to the values represented in the Table, crude gas is introduced into an absorption and regeneration column (2) via line (1) and washed therein. The first exhaust gas stream (5) from the regeneration, which consists of about 76 vol-% hydrocarbon and about 13 vol-% CO₂ with small amounts of mercaptans and H₂S, is directly introduced into a Claus plant (14).

A second sour gas stream (4) with a low H₂S concentration (20.5 vol-%) is introduced into an absorption plant (15), where it is fortified with a non-loaded or hardly loaded solvent from lines (26) and (27). From the absorption plant (15), the solvent (16) loaded with H₂S is introduced into a regeneration plant (17). The gas with about 96 vol-% CO₂ and 0.2 vol-% mercaptan from the absorption plant (15) is supplied to a hydrogenation (22) via line (18). From the regeneration (17), sour gas with a high H₂S concentration (43.8 vol-%) is introduced into the Claus plant (14) via line (19).

From the absorption and regeneration column (2), a third gas stream (3) with a mercaptan content of about 0.01 vol-% is withdrawn, cooled (6) and supplied to an adsorption (8) via line (7). From this adsorption (8), the valuable gas is supplied to further processes, e.g. a liquefaction, via line (9). The mercaptan-containing gas stream is subjected to a physical washing stage, from which part of the valuable gas is recovered as fuel gas via line (12), and via line (13) the highly concentrated mercaptan gas is supplied to the Claus plant (14). The mercaptan stream is recovered in the regeneration of the Purisol solvent. The amount is small, but with a very high mercaptan concentration of about 54 vol-%. In the Claus plant (14), the mercaptan is burnt completely. The resulting SO₂ is reacted with the H₂S from the sour gas of line (19) to obtain sulfur. The liquid sulfur obtained is withdrawn via line (21) and supplied to a further use. The residual gas of the Claus plant chiefly consists of the components CO₂, N₂ and H₂O and is withdrawn via line (20). 

1. A process of removing mercaptan from crude gas, in which crude gas is introduced into an absorption and regeneration column (2) and washed therein, three gas streams (3, 4, 5) being withdrawn from this absorption and regeneration column (2), a first exhaust gas stream (5) being introduced into a Claus plant (14), a second gas stream (4) with a H₂S concentration of up to 30 vol-% being introduced into another absorption plant (15), characterized in that a third gas stream (3), the valuable gas with the mercaptans, is cooled (6) and supplied to an adsorption plant (8), that from this adsorption plant (8) the cleaned valuable gas (9) is withdrawn, and a mercaptan-containing gas stream (10) is subjected to a washing stage (11), and that this concentrated mercaptan-containing gas (13) is supplied to the Claus plant (14).
 2. The process as claimed in claim 1, characterized in that the washing stage (11) is a physical washing stage.
 3. The process as claimed in claim 1, characterized in that the second gas stream (4) is fortified in an absorption plant (15), the resulting solution (16) is supplied to a regeneration (17), and the resulting gas (19) concentrated with H₂S is supplied to the Claus plant (14).
 4. The process as claimed in claim 1, characterized in that from the absorption plant (24), which is disposed behind the hydrogenation (22) of the residual Claus gas (20), the H₂S-containing solution (26) is withdrawn and introduced into the absorption plant (15) for the sour gas.
 5. The process as claimed in claim 1, characterized in that the gas from the absorption of the fortification (15) is introduced into the hydrogenation (22) and then into the absorption plant (24). 